Benzotriazole and oxanilide UV absorber hydrazides

ABSTRACT

Hydrazide functionalized benzotrialzole and oxanilide ultraviolet absorbers (Formulas I and II) useful for stabilizing coreactive or inert polymeric compositions and novel intermediates (Formula III used to make certain types of compounds of Formula I) are disclosed and have the general formulas: ##STR1## wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , X, Y, all substituents thereof, and n are set forth in the Summary of the Invention.

CROSS-REFERENCE TO RELATED APPLICATION

This is a continuation-in-part of U.S. patent application Ser. No.84,608, filed Aug. 12, 1987.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to compounds which incorporate both anultraviolet light stabilizer and a hydrazide heat stabilizer functionalgroups. The ultraviolet light absorber can be either a2-(2-hydroxyphenyl)-2H-benzotriazole derivative or an oxanilidederivative.

2. Description of the Prior Art

In addition to activity as a stabilizer on a molar basis (i.e., UVabsorber, heat stabilizer, etc.), a successful stabilizer additive musthave both excellent compatibility with and/or solubility in numerouspolymer substrates, along with superior resistance to loss from thestabilized composition during processing and end-use application. Manystabilizer additives exhibit limited compatibility in certainsubstrates, and excessive tendency to exude, sublime and/or volatilizeduring weathering or processing of stabilized compositions, particularlywhen use conditions require exposure to elevated temperatures. Becauseof this problem, several attempts have been made to increase thecompatibility and reduce the volatility of such stabilizer additives bymodifying their structure.

While improvements have been noted over the years, experience has shownthat state-of-the-art stabilizers do not exhibit the desired combinationof properties in all resins and that new polymeric compositions continueto invoke additional structural modifications on any potential heatand/or light stabilizer intended for use. Two examples of this would bein "high solids" coatings which require greater solubility of thestabilizer due to the use of less solvent, and in engineeringthermoplastics where processing temperatures (in excess of 250° C.)require the use of stabilizers with high thermal stability and very lowvolatility. No one stabilizer to date provides the properties necessaryfor universal application and there is a constant commercial need fornew stabilizers offering a range of property advantages.

Systems which incorporate UV absorbers and other functional groups areknown. Multifunctional stabilizers have been prepared by reacting onetype of stabilizer with another to obtain a higher molecular weightcompound having dual functionality or by reacting two or morestabilizers with a multifunctional coupling agent in a stepwise fashion.

Japanese Pat. No. 73/43568 (Chemical Abstracts 81:122589s) discloses theuse of a 2-(2-hydroxyphenyl)-2H-benzotriazole UV absorber and ahydrazide to give enhanced resistance to photodegradation ofpolyurethane copolymer fibers.

U.S. Pat. No. 4,785,063 discloses certain benzotriazole hydrazides and acopolymerizable acyl hydrazide derivative.

SUMMARY OF THE INVENTION

The novel compounds of this invention have the following generalformulas: ##STR2## where

R is alkyl of 1-4 carbons or phenyl.

R¹ is hydrogen, substituted or unsubstituted aliphatic of 1-8 carbons,substituted or unsubstituted alkoxy of 1-8 carbons, substituted orunsubstituted alkoxycarbonyl of 2-8 carbons, alkylaminocarbonyl of 2-5carbons, dialkylaminocarbonyl of 3-9 carbons, substituted orunsubstituted N-(alkyl)-N-(aryl)aminocarbonyl of 8-15 carbons,alkoxysulfonyl of 1-4 carbons, --C(═0)--OH--, --C(═O)NH₂, or --S(═O)₂--OH. Preferably, R¹ is hydrogen, substituted or unsubstituted aliphaticof 1-8 carbons, substituted or unsubstituted alkoxy of 1-8 carbons,methoxycarbonyl, ethoxycarbonyl, carboxy, chloro or S(═O)₂ --OH. Mostpreferably, R¹ is hydrogen, alkyl of 1-4 carbons, methoxy, ethoxy,chloro, or carboxy.

R² is hydrogen, substituted or unsubstituted aliphatic of 1-8 carbons,substituted or unsubstituted aryl of 6-14 carbons, substituted orunsubstituted araliphatic of 7-22 carbons, substituted or unsubstitutedalkoxy of 1-8 carbons, alkylaminocarbonyl of 2-5 carbons,dialkylaminocarbonyl of 3-9 carbons, or substituted or unsubstitutedN-(alkyl)-N-(aryl)aminocarbonyl of 8-15 carbons. Preferably, R² ishydrogen, substituted or unsubstituted aliphatic of 1-8 carbons, orsubstituted or unsubstituted araliphatic of 7-9 carbons. Mostpreferably, R² is methyl, ethyl, t-butyl, t-octyl, or1-methyl-1-phenylethyl.

R³ is hydrogen, substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted araliphatic of 7-22 carbons, or substitutedor unsubstituted alicyclic of 5-12 carbons. Preferably, R³ is hydrogen.

R⁴, R⁵, R⁶ and R⁷ are independently hydrogen, hydroxy, substituted orunsubstituted aliphatic of 1-8 carbons, substituted or unsubstitutedaryl of 6-14 carbons, substituted or unsubstituted araliphatic of 7-22carbons, substituted or unsubstituted alkoxy of 1-12 carbons orsubstituted or unsubstituted alkylthio of 1-12 carbons, chloro, bromo,or substituted or unsubstituted alkoxycarbonyl of 2-8 carbons.Preferably, R⁴, R⁵, R⁶ and R⁷ are independently hydrogen, hydroxy, alkylof 1-8 carbons, alkoxy of 1-8 carbons, alkylthio of 1-8 carbons, chloro,bromo, or alkoxycarbonyl of 2-8 carbons. Most preferably, R⁴, R⁵, R⁶ andR⁷ are independently hydrogen, hydroxy, alkyl of 1-8 carbon, alkoxy of1-4 carbons, alkylthio of 1-4 carbons, methoxycarbonyl orethoxycarbonyl.

X is X_(a) when attached to ring A, X_(b) when attached to ring B andX_(e) when attached to either ring E.

X_(a) is a direct bond.

X_(b) and X_(e) are divalent radicals of formula --Z_(x) --R⁸--{--N(R⁹)--[C(═O)]_(y) --R¹⁰ --)_(z) --.

Z is --O--, --N(R¹¹)--, --S--, or --S(═O)₂ --.

x, y and z are independently 0 or 1.

R⁸ is a direct bond or substituted or unsubstituted alkylene diradicalof 1-4 carbons. Preferably, R⁸ is a direct bond, methylene or1,2-ethanediyl.

R⁹ is hydrogen, substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted alicyclic of 5-12 carbons, substituted orunsubstituted aryl of 6-14 carbons, or substituted or unsubstitutedaraliphatic of 7-22 carbons. Preferably, R⁹ is hydrogen, substituted orunsubstituted aliphatic of 1-12 carbons, substituted or unsubstitutedalicyclic of 5-8 carbons, substituted or unsubstituted phenyl, orsubstituted or unsubstituted araliphatic of 7-9 carbons. Mostpreferably, R⁹ is selected from hydrogen, substituted or unsubstitutedaliphatic of 1-10 carbons, substituted or unsubstituted cyclohexyl,substituted or unsubstituted phenyl, or substituted or unsubstitutedaraliphatic of 7-14 carbons.

R¹⁰ is a direct bond, substituted or unsubstituted aliphatic diradicalof 1-20 carbons, substituted or unsubstituted aryl diradical of 6-12carbons, substituted or unsubstituted alicyclic diradical of 5-12carbons, or substituted or unsubstituted araliphatic diradical of 7-22carbons. Preferably, R¹⁰ is a direct bond, aliphatic diradical of 1-8carbons, 1,3-phenylene diradical or 1,4-phenylene diradical. Mostpreferably, R¹⁰ is a direct bond or alkylene diradical of 1-8 carbons.

R¹¹ independently is any of the groups of R⁹.

n is 1 or 2.

When n is 1, Y is ##STR3##

When n is 2, Y is ##STR4##

R¹² is hydrogen, substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted alicyclic of 5-12 carbons, substituted orunsubstituted aryl of 6-14 carbons, or substituted or unsubstitutedaraliphatic of 7-22 carbons. Preferably, R¹² is hydrogen, substituted orunsubstituted aliphatic of 1-12 carbons, substituted or unsubstitutedalicyclic of 5-8 carbons, substituted or unsubstituted phenyl, orsubstituted or unsubstituted araliphatic of 7-9 carbons. Mostpreferably, R¹² is hydrogen, substituted or unsubstituted aliphatic of1-10 carbons, substituted or unsubstituted cyclohexyl, substituted orunsubstituted phenyl, or substituted or unsubstituted araliphatic of7-14 carbons.

R¹³ is hydrogen, substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted alicyclic of 5-12 carbons, or substitutedor unsubstituted araliphatic of 7-22 carbons, and when alicyclic, R¹³may optionally contain 1-6 heteroatoms --O--, --S-- or --N(R²¹)--, withthe proviso that multiple heteroatoms must be separated from each otherand the chain ends by at least one carbon atom. Preferably, R¹³ ishydrogen, substituted or unsubstituted aliphatic of 1-12 carbons,substituted or unsubstituted alicyclic of 5-8 carbons, substituted orunsubstituted phenyl, or substituted or unsubstituted araliphatic of 7-9carbons, and when alicyclic, R¹³ may optionally contain 1 or 2heteroatoms --O-- and --N(R²¹)--, with the proviso that multipleheteroatoms are separated from each other and the chain ends by at leastone carbon atom. Most preferably, R¹³ is hydrogen, substituted orunsubstituted aliphatic of 1-10 carbons, substituted or unsubstitutedcyclohexyl, substituted or unsubstituted phenyl, or substituted orunsubstituted araliphatic of 7-14 carbons, and when alicyclic, R¹³ issubstituted 2,2,6,6-tetraalkyl-4-piperidinyl.

Q is --C(═O)-- except when x and z are 0, --S(═O)₂ --, --C(═O)--O--,--[C(═O)]₂ --O--, --C(═O)--N(R²²)--, --[C(═O)]₂ --N(R²²)--,--C(═S)--N(R²²)--, --C(═O)--R¹⁷ --C(═O)--N(R²²)--, or, when n is 1, adirect bond between the nitrogen and R¹³. Preferably, Q is --C(═O)--except when x and z are 0, --C(═O)--O--, --[C(═O)]₂ --O--,--C(═O)--N(R²²)--, --[C(═O)]₂ --N(R²²)--, or, when n is 1, a direct bondbetween the nitrogen and R¹³.

R¹⁴ and R¹⁵ are independently hydrogen, substituted or unsubstitutedaliphatic of 1-20 carbons, substituted or unsubstituted alicyclic of5-12 carbons, substituted or unsubstituted aryl of 6-14 carbons, orsubstituted or unsubstituted araliphatic of 7-22 carbons, or R¹⁴ and R¹⁵may be linked together to form a substituted or unsubstituted alicyclicring of 5-12 carbons or may be linked together through a heteroatom--N(R²¹)--, --O-- or --S-- to form a heterocyclic ring of 5-12 atoms.Preferably, R¹⁴ and R¹⁵ are independently substituted or unsubstitutedaliphatic of 1-8 carbons, substituted or unsubstituted alicyclic of 5-8carbons, substituted or unsubstituted aryl of 6-12 carbons, andsubstituted or unsubstituted araliphatic of 7-14 carbons, and may belinked together to form a substituted or unsubstituted cyclohexyl ringor a substituted or unsubstituted 2,2,6,6-tetraalkyl-4-piperidine ring.Most preferably, R¹⁴ and R¹⁵ are independently aliphatic of 1-8 carbons,alicyclic of 5-8 carbons or may be linked together to form a substitutedor unsubstituted cyclohexyl ring or a 2,2,6,6-tetramethyl-4-piperidinylring.

R¹⁶ is a substituted or unsubstituted aliphatic diradical of 2-200carbons with the proviso that when x and z are 0 R¹⁶ is not1,2-ethenediyl, substituted or unsubstituted aryl diradical of 6-14carbons, substituted or unsubstituted alicyclic diradical of 5-12carbons, or substituted or unsubstituted araliphatic diradical of 7-22carbons, and the diradical may optionally contain 1-6 heteroatoms --O--,--S-- or --N(R²¹)--, with the provisos that (a) multiple heteroatomsmust be separated from each other and the diradical ends by at least onecarbon atom, and (b) the cyclic group formed contains 5 or 6 atoms inthe ring. Preferably, R¹⁶ is a substituted or unsubstituted aliphaticdiradical of 2-30 carbons, substituted or unsubstituted ortho-phenylene,substituted or unsubstituted alicyclic diradical of 6-8 carbons and thediradical may optionally contain 1 or 2 heteroatoms --O-- or --N(R²¹)--,with the provisos stated above. Most preferably, R¹⁶ is a substituted orunsubstituted aliphatic diradical of 2-20 carbons.

R¹⁷ is a substituted or unsubstituted aliphatic diradical of 1-200carbons, substituted or unsubstituted aryl diradical of 6-14 carbons,substituted or unsubstituted alicyclic diradical of 5-12 carbons, orsubstituted or unsubstituted araliphatic diradical of 7-22 carbons, andthe diradical may optionally contain 1-6 heteroatoms --O--, --S--, or--N(R²¹)--, with the proviso that multiple heteroatoms must be separatedfrom each other and the diradical ends by at least one carbon atom.Preferably, R¹⁷ is a substituted or unsubstituted aliphatic diradical of2-18 carbons, substituted or unsubstituted phenylene, substituted orunsubstituted alicyclic diradical of 6-8 carbons, and the diradical mayoptionally contain 1 or 2 heteroatoms --O-- or --N(R²¹)--, with theproviso stated above. Most preferably, R¹⁷ is a substituted orunsubstituted aliphatic diradical of 2-8 carbons.

R¹⁸ is hydrogen, substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted araliphatic of 7-22 carbons, or substitutedor unsubstituted alicyclic of 5-12 carbons. Preferably, R¹⁸ is hydrogen,substituted or unsubstituted aliphatic of 1-8 carbons, substituted orunsubstituted araliphatic of 7-8 carbons, or substituted orunsubstituted alicyclic of 5-8 carbons. Most preferably, R¹⁸ ishydrogen, substituted or unsubstituted aliphatic of 1-10 carbons,substituted or unsubstituted cyclohexyl or benzyl.

R¹⁹ is R¹³ --NH-- or OM.

R²⁰ is a substituted or unsubstituted aliphatic diradical of 1-20carbons, substituted or unsubstituted aryl diradical of 6-12 carbons,substituted or unsubstituted alicyclic diradical of 5-14 carbons, orsubstituted or unsubstituted araliphatic diradical of 7-22 carbons.Preferably, R²⁰ is a substituted or unsubstituted aliphatic diradical of2-12 carbons, substituted or unsubstituted aryl diradical of 6-12carbons, substituted or unsubstituted alicyclic diradical of 5-12carbons, or substituted or unsubstituted araliphatic diradical of 7-12carbons. Most preferably, R²⁰ is a substituted or unsubstitutedaliphatic diradical of 2-10 carbons, substituted or unsubstitutedphenylene, substituted or unsubstituted alicyclic diradical of 5-8carbons, or substituted or unsubstituted araliphatic diradical of 7-12carbons.

R²¹ is hydrogen, aliphatic of 1 to 8 carbons, aliphatic acyl of 2-6carbons, or substituted or unsubstituted benzoyl. Preferably, R²¹ ismethyl or hydrogen.

As used herein, the term "acyl" refers to a radical generated from acarboxylic acid by removal of the OH group to provide a free valence

on the C(═O) group, for example DC(═O)--OH would become the DC(═O)--substituent, referred to generally as a D acyl group.

R²² is hydrogen or aliphatic of 1 to 4 carbons. Preferably, R²² ismethyl or hydrogen.

M is hydrogen, sodium ion, potassium ion or ammonium ion. Preferably, Mis hydrogen or sodium ion. Most preferably, M is hydrogen.

Optional substituents for R¹, R², R³, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴,R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰ and R²¹ are independently one or more ofthe following: chloro, bromo, alkyl of 1-4 carbons, alkoxy of 1-8carbons, phenoxy, cyano, hydroxy, epoxy, carboxy, alkyoxycarbonyl of 2-6carbons, acyloxy of 1-4 carbons, acryloyl, acryloyloxy, methacryloyl,methacryloyloxy, hydroxymethyl, hydroxyethyl, alkylthio of 1-4 carbons,or trialkoxysilyl of 3-12 carbons.

Additional optional substituents for R¹³ are aliphatic of 1-20 carbons,cycloaliphatic of 5-12 carbons, aryl of 6-14 carbons, aralkyl of 7-22carbons, alkoxy of 1-20 carbons, cycloalkoxy of 5-12 carbons, aryloxy of6-14 carbons, aralkoxy of 7-15 carbons, aliphatic acyloxy of 2-20carbons, alicyclic acyloxy of 6-13 carbons, aryl acyloxy of 7-15carbons, or araliphatic acyloxy of 8-16 carbons.

Additional optional substituents for R¹⁷ and R¹⁸ are independently alkylof 5-180 carbons, alkylthio of 5-180 carbons, aralkylthio of 7-20carbons, arylthio of 6-20 carbons, alkenyl of 2-180 carbons,cycloalkenyl of 5-12 carbons, aryl of 6-16 carbons, aralkyl of 7-17carbons, aryloxy of 6-16 carbons, alkoxycarbonyl of 7-10 carbons, or(alkoxycarbonyl)alkylthio of 3-30 carbons.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS General Formula

The novel compounds of Formulas I and II are UV absorber compounds.

The compounds of Formula III are ester precursors used as intermediatesto make certain hydrazides of Formula I having corresponding structuresand substituents. The compounds of the present invention have thefollowing general formulas: ##STR5## where R, R¹ , R², R³, R⁴, R⁵, R⁶,R⁷, R⁸, R⁹, X and Y, all substituents thereof, and n are as previouslydefined.

Generic Group Examples

As substituted or unsubstituted aliphatic of 1-8 carbons, R¹, R², R⁴,R⁵, R⁶, R⁷ and R²¹ are, independently, for example, methyl,2-hydroxyethyl, ethyl, 2-acetoxyethyl, isopropyl, 2-chloroethyl, allyl,methallyl, pentyl, 2-(methacryloyloxy)ethyl, 3-pentyl, t-butyl, hexyl,octyl, or t-octyl.

As substituted or unsubstituted aliphatic of 1-20 carbons, R³, R⁹, R¹¹,R¹², R¹³, R¹⁴, R¹⁵, R¹⁸ and R¹⁹ are, independently, for example, methyl,ethyl, n-propyl, isopropyl, butyl, allyl, n-pentyl, 2-bromoethyl, hexyl,heptyl, octyl, nonyl, decyl, propargyl, octadecyl, dodecyl, isododecyl,2-acetoxyethyl, tetradecyl, 2-methallyl, 2-hexenyl, 10-undecenyl,2-dodecenyl, n-butyl, 2-hydroxyethyl, 2-butenyl, 2-hydroxyhexadecyl,2-hydroxypropyl, 2-hexenyl, 10-undecenyl, 2-hydroxydodecyl,2-hydroxy-5-hexenyl, 2-hydroxyhexyl, 2-hydroxydecyl, 2-hydroxyoctadecyl,2-hydroxy-3-(methacryloyloxy)propyl, 2-hydroxy-3-(acryloyloxy)propyl,2-hydroxy-3-phenoxypropyl, 2-hydroxy-3-(4-methoxyphenoxy)propyl,2-hydroxy-3-isopropoxypropyl, 2-hydroxy-3-methoxypropyl,2-hydroxy-3-(2-ethylhexyloxy)propyl, 3-(trimethoxysilyl)propyl,2-hydroxy-3-(cyclohexyloxy)propyl, 2-hydroxy-3-(benzyloxy)propyl,2-hydroxy-3-(benzoyloxy)propyl, 2-hydroxy-3-dodecyloxypropyl,2-hydroxybutyl, 1-methyl-2-hydroxypropyl, cyanomethyl, 2,3-epoxypropyl,or 2-(dimethylamino)ethyl.

As substituted or unsubstituted alkoxy of 1-8 carbons, R¹ and R² are,independently, for example, methoxy, ethoxy, 2-ethylhexyloxy,isopropoxy, 2-hydroxypropoxy, 2-(acyloyloxy)ethoxy, or sec-butoxy.

As substituted or unsubstituted alkoxycarbonyl of 2-8 carbons, R¹, R⁴,R⁵ and R⁷ are, independently, for example, methoxycarbonyl,ethoxycarbonyl, 2-hydroxyethylcarbonyl, allyloxycarbonyl, orbutoxycarbonyl.

As alkylaminocarbonyl of 2-5 carbons, dialkylaminocarbonyl of 3-9carbons and substituted or unsubstituted N-(aryl)-N-(alkyl)aminocarbonylof 8-15 carbons, R¹ and R² are, independently, for example,methylaminocarbonyl, ethylaminocarbonyl, butylaminocarbonyl,N-(4-methylphenyl)-N-methylaminocarbonyl,N-phenyl-N-methylaminocarbonyl, N-(2-ethoxyphenyl)-N-ethylaminocarbonyl,N-(3-isopropenylphenyl)-N-butylaminocarbonyl, dimethylaminocarbonyl, ordibutylaminocarbonyl.

As alkoxysulfonyl of 1-4 carbons, R¹ is, for example, methoxysulfonyl,or butoxysulfonyl.

As substituted or unsubstituted alkoxy of 1-12 carbons or substituted orunsubstituted alkylthio of 1-12 carbons, R⁴, R⁵, R⁶ and R⁷ are,independently, for example, methoxy, ethoxy, 2-ethylhexyloxy,isopropoxy, 2-hydroxypropoxy, 2-(acyloyloxy)ethoxy, sec-butoxy,dodecyloxy, methylthio, ethylthio, isopropylthio, butylthio,dodecylthio, octylthio, or hexylthio.

As substituted or unsubstituted alicyclic of 5-12 carbons, R³, R⁹, R¹¹,R¹², R¹³, R¹⁴, R¹⁵, R¹⁸ and R¹⁹ are, independently, for example,cyclohexyl, trimethylcyclohexyl, cyclooctyl, cyclododecyl,4-t-butylcyclohexyl, 2-hydroxycyclododecyl, 3-cyclohexenyl,2-hydroxycyclohexyl, 2-hydroycyclopentyl, cyclododecyl,4-octylcyclohexyl, or 2-methyl-4-octylcyclohexyl.

As substituted or unsubstituted aryl of 6-14 carbons, R², R⁴, R⁵, R⁶,R⁷, R⁹, R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁹ are, independently, for example,phenyl, tolyl, 4-chlorophenyl, isopropylphenyl, isopropenylphenyl,anisyl, 3,5-di-t-butyl-4-hydroxyphenyl, 3,5-di-t-amyl-4-hydroxyphenyl,4-vinylphenyl, 3-t-butyl-5-methyl-4-hydroxyphenyl, naphthyl,3-methyl-5-t-butyl-4-hydroxyphenyl, 3,4,5-trimethoxyphenyl, or4-di(methylamino)phenyl.

As substituted or unsubstituted araliphatic of 7-22 carbons, R², R³, R⁴,R⁵, R⁶, R⁷, R⁹, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁸ and R¹⁹ are, independently,for example, benzyl, 3-methylbenzyl, 4-t-butylbenzyl, cinnamyl,3,5-di-t-butyl-4-hydroxybenzyl, 2-hydroxy-2-phenylethyl, 2-phenylethyl,cumyl, trimethylbenzyl, 4-octyloxybenzyl, naphthylmethyl, or(4-dodecylphenyl)methyl, 2-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl,2-(3,5-di-t-amyl-4-hydroxyphenyl)ethyl, or2-(3-t-butyl-5-methyl-4-hydroxyphenyl)ethyl.

As substituted or unsubstituted alkylene diradical of 1-4 carbons, R⁸is, for example, methylene, 1,2-ethanediyl, 1,1-ethanediyl,2-hydroxy-1,3-propanediyl, 1,2-propanediyl, 1,3-propanediyl,2-methoxy-1,3-propanediyl, 1,2-butanediyl, 1,3-butanediyl, or1,4-butanediyl.

As substituted or unsubstituted aliphatic diradical of 1-20 carbon,substituted or unsubstituted aryl diradical of 6-12 carbons, substitutedor unsubstituted alicyclic diradical of 5-12 carbons and substituted orunsubstituted araliphatic diradical of 7-22 carbons, R¹⁰ is, forexample, methylene, 1,2-ethanediyl, 1,2-propanediyl, 1,3-propanediyl,1,4-butanediyl, 1,18-octadecanediyl, 2,2-dimethyl-1,3-propanediyl,2-methylpentane-2,4-diyl, 1,10-decanediyl, 1,12-dodecanediyl,3-oxapentane-1,5-diyl, 4-oxaheptane-1,7-diyl, 3,6-dioxaoctane-1,8-diyl,4,9-dioxadodecane-1,12-diyl, 4-methyl-4-azaheptane-1,4-diyl,3,6-diaza-3,6-dimethyl-1,8-octanediyl, 3-methyl-3-azapentane-1,5-diyl,1,2-cyclohexanediyl, 1,4-cyclohexanediyl, 1,2-ethenediyl,1,2-propenediyl, 1-chloro-1,2-ethenediyl, 1-phenyl-1,2-ethenediyl,1,3-hexanediyl, 1,2-cyclohexanediyl, 1,2-phenylene,4-methyl-4-cyclohexene-1,2-diyl, 4-cyclohexene-1,2-diyl,4-methylcyclohexane-1,2-diyl, 4-carboxy-1,2-phenylene,4-methoxycarbonyl-1,2-phenylene, propane-2,2-bis[4-cyclohexyl],3-oxapentane-1,5-diyl, methylenebis[4 -cyclohexyl], 1,2-, 1,3-, or1,4-phenylene, 1,2-, 1,3-, or 1,4 -phenylenebis(methyl),biphenyl-4,4'-diyl, biphenyl-3,3'-diyl, biphenyl- 3,4'-diyl, ormethylenebis[phenylene].

When alicyclic and optionally containing 1-6 heteroatoms --O--, --S--and --N(R²¹)--, with the proviso that multiple heteroatoms must beseparated from each other and the chain ends by at least one carbonatom, R¹³ is, for example, 2,2,6,6-tetramethyl-4-piperidinyl,2,6-diethyl-1,2,3,6-tetramethyl-4-piperidinyl,1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl and1-(4-methylbenzoyl)-2,6-dimethyl-2,6-dipropyl-3-ethyl-4-piperidinyl.

When linked together to form a substituted or unsubstituted alicyclicring of 5-12 atoms or when linked together through a heteroatom--N(R²¹)--, --O-- or --S--, R¹⁴ and R¹⁵ are, for example, cyclopentyl,cyclohexyl, cycloheptyl, 4-t-butylcyclohexyl, 2-methylcyclohexyl,cyclooctyl, 2,2,6,6-tetramethyl-4-piperidinyl,2,6-diethyl-2,3,6-trimethyl-4-piperidinyl,1,2,2,6,6-pentamethyl-4-piperidinyl,1-ethyl-2,2,6,6-tetramethyl-4-piperidinyl, 4-oxacyclohexyl, and4-thiacyclohexyl.

As substituted or unsubstituted aliphatic diradical of 2-200 carbons,substituted or unsubstituted aryl diradical of 6-14 carbons, substitutedor unsubstituted alicyclic diradical of 5-12 carbons, or substituted orunsubstituted araliphatic diradical of 7-22 carbons, any of which mayoptionally contain 1-6 heteroatoms --O--, --S--, or --N(R²¹)--, with theprovisos that (a) multiple heteroatoms must be separated from each otherby at least one carbon atom and (b) the cyclic group formed contains 5or 6 atoms in the ring, R¹⁶ is, for example, 1,2-ethanediyl,1,2-ethenediyl except when x and z are 0, 1,3-propanediyl,1,2-propenediyl, 2-thiapropane-1,3-diyl, 2-oxapropane-1,3-diyl,1-chloro-1,2-ethenediyl, 1-phenyl-1,2-ethenediyl, 1,3-hexanediyl,2-azapropane-1,3-diyl, 2-methyl-2-azapropane-1,3-diyl,1,2-cyclohexanediyl, 1,2-phenylene, 4-methyl-4-cyclohexene-1,2-diyl,4-cyclohexene-1,2-diyl, 4-methylcyclohexane-1,2-diyl,norbornane-2,3-diyl, 5-norbornene-2,3-diyl,bicyclo[2.2.2]octane-2,3-diyl, bicyclo[2.2.2]oct-5-ene-2,3-diyl,bicyclo[2.2.1]heptane-1,2-diyl, bicyclo[2.2.1]heptane-1,2-diyl,4-carboxy-1,2-phenylene, 4-methoxycarbonyl-1,2-phenylene;1-(substituted)ethane-1,2-diyl, wherein the substituent is hydrogen,chloro, phenyl, methyl, ethyl, propyl, butyl, hexyl, octyl, decyl,dodecyl, hexadecyl, octadecyl, hexenyl, isohexenyl, diisobutenyl,decenyl, dodecenyl, isododecenyl, octenyl, nonenyl, tetradecenyl,hexadecenyl, octadecenyl, isooctadecenyl, triacontenyl, orpolyisobutenyl; 1-(substituted)ethane-1,2-diyl,5-(substituted)norbornane-2,3-diyl,5-(substituted)bicyclo[2.2.2]octane-2,3-diyl, or4-(substituted)cyclohexane-1,2-diyl, wherein the substituent ismethylthio, ethylthio, butylthio, hexylthio, octylthio, hexadecylthio,octadecylthio, 2-hydroxyethylthio, phenylthio, benzylthio,(3,5-di-t-butyl-4-hydroxy)phenylthio, or(3-t-butyl-5-methyl-4-hydroxyphenyl)benzylthio.

As substituted or unsubstituted aliphatic diradical of 1-200 carbons,substituted or unsubstituted aryl diradical of 6-14 carbons, substitutedor unsubstituted alicyclic diradical of 5-12 carbons, or substituted orunsubstituted araliphatic diradical of 7-22 carbons, any of which mayoptionally contain 1-6 heteroatoms --O--, --S--, or --N(R²¹)--, with theproviso that multiple heteroatoms must be separated from each other byat least one carbon atom, R¹⁷ is, for example, methylene,1,2-ethanediyl,1,2-ethenediyl, 1,3 -propanediyl, 1,2-propenediyl,2-thiapropane-1,3-diyl, 3-thiapentane-1,2-diyl, 2-oxapropane-1,3-diyl,1-chloro-1,2-ethenediyl, 1-phenyl-1,2-ethenediyl, 1,3-hexanediyl,2-azapropane-1,3-diyl, 2-methyl-2-azapropane-1,3-diyl,1,2-cyclohexanediyl, 1,2-phenylene, 4-methyl-4-cyclohexene-1,2-diyl,4-cyclohexene-1,2-diyl, 4-methylcyclohexane-1,2-diyl,norbornane-2,3-diyl, 5-norbornene-2,3-diyl,bicyclo[2.2.2]octane-2,3-diyl, bicyclo[2.2.2]oct-5-ene-2,3-diyl,bicyclo[2.2.1]heptane-1,2-diyl, bicyclo[2.2.1]heptane-1,2-diyl,4-carboxy-1,2-phenylene, 4-methoxycarbonyl-1,2-phenylene,propane-2,2-bis[4-cyclohexyl], 3-oxapentane-1,5-diyl,methylenebis[4-cyclohexyl], 1,2-, 1,3-, or 1,4-phenylene, 1,2-, 1,3-, or1,4-phenylenebis(methyl), or 2,5-diazahexane-1,6-diyl,biphenyl-4,4'-diyl, biphenyl-3,3'-diyl, biphenyl-3,4'-diyl,methylenebis[phenylene]; 1-(substituted)ethane-1,2-diyl, wherein thesubstituent is hydrogen, chloro, phenyl, methyl, ethyl, propyl, butyl,hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, hexenyl, isohexenyl,diisobutenyl, decenyl, dodecenyl, isododecenyl, octenyl, nonenyl,tetradecenyl, hexadecenyl, octadecenyl, isooctadecenyl, triacontenyl, orpolyisobutenyl; 1-(substituted)ethane-1,2-diyl,5-(substituted)norbornane-2,3-diyl,5-(substituted)bicyclo[2.2.2]octane-2,3-diyl, or4-(substituted)cyclohexane-1,2-diyl, wherein the substituent ismethylthio, ethylthio, butylthio, hexylthio, octylthio, hexadecylthio,octadecylthio, 2-hydroxyethylthio, phenylthio, benzylthio,(3,5-di-t-butyl-4-hydroxy)phenylthio, or(3-t-butyl-5-methyl-4-hydroxyphenyl)benzylthio.

As substituted or unsubstituted aliphatic diradical of 1-20 carbons,substituted or unsubstituted aryl diradical of 6-12 carbons, substitutedor unsubstituted alicyclic diradical of 5-12 carbons, or substituted orunsubstituted araliphatic diradical of 7-22 carbons, R²⁰ is, forexample, methylene, ethane-1,2-diyl, ethene-1,2-diyl, propane-1,3-diyl,propene-1,2-diyl, 2-thiapropane-1,3-diyl, 2-oxapropane-1,3-diyl,hexane-1,3-diyl, 2-azapropane-1,3-diyl, 2-methyl-2-aza-propane-1,3-diyl,cyclohexane-1,2-diyl, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene,hexane-1,6-diyl, octane-1,8-diyl, decane-1,10-diyl, dodecane-1,12-diyl,3-hexene-1,6-diyl, 4-methyl-1,2-phenylene, 4-chloro-1,2-phenylene, 4-methylcyclohexane-1,2-diyl, cyclohexane-1,2-diyl,4-methyl-4-cyclohexene-1,2-diyl, toluene-alpha,2-diyl,toluene-alpha,3-diyl, toluene-alpha,4-diyl, or isophoronediyl.

As aliphatic acyl of 2-6 carbons and substituted or unsubstitutedbenzoyl, R²¹ is, for example, acetyl, propionyl, pivaloyl, isobutanoyl,hexanoyl, benzoyl, 4-hydroxybenzoyl, 4-methylbenzoyl,2,4-dichlorobenzoyl, 3,5-di-t-butyl-4-hydroxybenzoyl, or3-isopropenylbenzoyl.

List of Example Compounds

Examples of stabilizer compounds of the present invention include thefollowing, non-limiting list of compounds:

1.10-[2-hydroxy-3-(2H-benzotriazol-2-yl)-5-methylphenyl[-5,6,9-triaza-4,7,8-trioxodecanoicacid, sodium salt

2.1,20-di[3-(2H-benzotriazol-2-yl)-4-hydroxy-5-t-butylphenyl]-4,5,7,14,16,17-hexaaza-3,6,15,18-tetraoxoecosane

3.1,18-di[2-hydroxy-3-(2H-benzotriazol-2-yl)-5-methylphenyl]-2,5,6,13,14,17-hexaaza-3,4,7,12,15,16-hexaoxooctadecane

4.1,16-di[3-hydroxy-4-(2H-benzotriazol-2-yl)phenoxy]-3,4,13,14-tetraaza-2,5,12,15-tetraoxo-6,11-dioxahexadecane

5.1,4-phenylenebis{N'-[4-([(2-hydroxy-3-(2H-benzotriazol-2-yl)-5-methylphenyl)methyl]amino)-4-oxobutanoyl]sulfonylhydrazide}

6.1,28-di[2-hydroxy-3-(2H-benzotriazol-2-yl)-5-methyl]-2,9,10,12,17,19,20,27-octaaza-3,8,21,26-tetraoxo-11,18-di(thioxo)octacosane

7N-[(2-hydroxy-3-(2H-benzotriazol-2-yl)-5-methylphenyl)methyl]hydrazinecarboxamide

8.2-{[2-hydroxy-3-(2H-benzotriazol-2-yl)-5-methylphenyl]methylamino}-2-oxoacetylhydrazide

93-{N-[2-hydroxy-3-(2H-benzotriazol-2-yl)-5-t-butylphenyl]methyl-N-methylamino}-3-oxo-N'-methylpropionylhydrazide

10.4-{N-[2-hydroxy-3-(5-chloro-2H-benzotriazol-2-yl)-5-ethylphenyl]methyl-N-butylamino}-4-oxo-N'-(benzoyl)butanoylhydrazide

11.4-{N-[2-hydroxy-3-(5-(ethoxycarbonyl)-2H-benzotriazol-2-yl)-5-t-amylphenyl]methyl-N-ethylamino}-4-oxo- N'-(ethylaminocarbonyl)butanoyl hydrazide

12.9-{[2-hydroxy-3-(5-[aminocarbonyl]-2H-benzotriazol-2-yl)-5-(1-methyl-1-phenylethyl)phenyl]methylamino}-9-oxo-N'-(diethylaminocarbonyl)nonanoylhydrazide

13.7-{[2-hydroxy-3-(5-[carboxy]-2H-benzotriazol-2-yl)-5-(1-ethylpentyl)-phenyl]methylamino}-7-oxo-4-thia-N'-(phenylsulfonyl)heptanoylhydrazide

14.3-[3-(2H-benzotriazol-2-yl)-4-hydroxy-5-t-octylphenyl]-N'-(propyl)propionylhydrazide

15.2-[3-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxy-5-t-butylphenyl]-N'-(ethoxycarbonyl)acetylhydrazide

16.5-[3-(5-[ethoxycarbonyl]-2H-benzotriazol-2-yl)-4-hydroxy-5-methylphenyl]-pentanoylhydrazide, 2,2,6,6-tetramethyl-4-piperidone hydrazone

17. 2-[3-hydroxy-4-(2H-benzotriazol-2-yl)phenoxy]-N'-methylacetylhydrazide

18.3-[3-hydroxy-4-(5-chloro-2H-benzotriazol-2-yl)phenylamino]-3-oxo-N'-(acetyl)propionylhydrazide

19.2-[3-hydroxy-4-(5-[ethoxycarbonyl]-2H-benzotriazol-2-yl)phenylthio]-N'-(butylaminocarbonyl)acetylhydrazide

20.5-{N-[3-hydroxy-4-(5-ethyl-2H-benzotriazol-2-yl)phenyl]-N-methylamino}-N'-(methoxycarbonyl)pentanoylhydrazide

21.N-{[3-hydroxy-4-(2H-benzotriazol-2-yl)phenylsulfinyl]butyl}-N-methylhydrazinecarboxamide

22.N-{2-[3-hydroxy-4-(5-chloro-2H-benzotriazol-2-yl)phenylsulfonyl]ethyl}-2-phenylhydrazinecarboxamide

23. 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazol-5-carboxylic hydrazide

24. 2-(2-hydroxy-5-t-butylphenyl)-6-chloro-2H-benzotriazol-5-carboxylichydrazide

25.2-[2-hydroxy-5-(1-methyl-1-phenylethyl)phenyl]-6-methyl-2H-benzotriazol-5-carboxylichydrazide

26. 2-(2-hydroxy-5-t-octylphenyl)-6-methoxy-2H-benzotriazol-5-carboxylichydrazide

27.2-(2-hydroxy-5-ethylphenyl)-6-butoxy-N'-acetyl-2H-benzotriazol-5-carboxylichydrazide

28.2-(2-hydroxy-5-propylphenyl)-6-(ethoxycarbonyl)-N'-benzoyl-2H-benzotriazol-5-carboxylichydrazide

29.2-(2-hydroxy-5-ethoxyphenyl)-6-(butylaminocarbonyl)-N'-methyl-2H-benzotriazol-5-carboxylichydrazide

30.2-(2-hydroxy-5-(dimethylaminocarbonyl)phenyl)-6-(diethylaminocarbonyl)-N'-phenyl-2H-benzotriazol-5-carboxylichydrazide

31.2-(2-hydroxy-5-butylphenyl)-6-(methoxysulfonyl)-N'-(ethoxycarbonyl)-2H-benzotriazol-5-carboxylichydrazide

32. 2(2-hydroxy-5-[octylaminocarbonyl]phenyl)-6-carboxy-N-(2-octylsuccinimido)-2H-benzotriazol-5-carbonamide

033.2-(2-hydroxy-5-t-amylphenyl)-6-(aminocarbonyl)-2H-benzotriazol-5-carboxylichydrazide, acetone hydrazone

34.2-(2-hydroxy-5-[phenyl]phenyl)-6-sulfo-N'-lauroyl-2H-benzotriazol-5-carboxylichydrazide.

35. 2-{(2-[(2-methoxyphenylamino)-2-oxoacetamido]phenoxy}acetylhydrazide

36.2-{4-[(2-methoxyphenylamino)-2-oxoacetamido]phenoxy}-N'-(butylaminocarbonyl)acetylhydrazide

37.2-{4-[(2-methoxyphenylamino)-2-oxoacetamido]phenoxy}-N'-(butylaminocarbonyl)acetylhydrazide

38.2-{4-[(2-ethoxyphenylamino)-2-oxoacetamido]phenoxy}-N-(succinimido)acetamide

39. 2-{2-[(2-ethylphenylamino)-2-oxoacetamido]phenoxy}acetyl hydrazide,acetone hydrazone

40.2-(2-[(2,4-dimethoxyphenylamino)-2-oxoacetamido]phenoxy}-N'-(benzoyl)acetylhydrazide

41. 2-{2-[(4-butylphenylamino)-2-oxoacetamido]phenoxy}-N'-phenylacetylhydrazide

42.2-{2-[(2,4-dimethylphenylamino)-2-oxoacetamido]phenoxy}-N'-(ethoxycarbonyl)acetylhydrazide

43. 2-{(2-[(2-methoxyphenylamino)-2-oxoacetamido]phenoxy}acetylhydrazide

44.1,16-di{(2-[(2-methoxyphenylamino)-2-oxoacetamido]phenyl}-2,3,5,12,14,15-hexaaza-1,4,1316-tetraoxohexadecane

45.2-{4-[(2-methoxy-5-octylphenylamino)-2-oxoacetamido]-phenylamino}acetylhydrazide

46.4-[{3-[(2-ethoxy-5-t-butylphenylamino)-2-oxoacetamido]phenylamino}-N'-(isopropoxycarbonyl)butanoylhydrazide

47. 4-[(2-ethoxy-5-methylphenylamino)-2-oxoacetamido]benzoyl hydrazide

48.3-{3-[(2-butoxyphenylamino)-2-oxoacetamido]phenylamino}-N'-(benzyl)propionylhydrazide

49.2-{3-[(2-hexoxyphenylamino)-2-oxoacetamido]phenylthio}-N'-ethylacetylhydrazide

50.1,22-di{3-[(2-ethoxyphenylamino)-2-oxoacetamido]-4-methylphenylamino}-7,8,15,16-tetraaza-1,6,9,14,17,22-hexaoxodocosane

51.3-{4-[(2-(ethylthio)phenylamino)-2-oxoacetamido]phenoxy}-N'-(3-carboxypropoxy)propionylhydrazide

52.2-{3-[(2-hydroxyphenylamino)-2-oxoacetamido]phenylamino}-N'-(2-dodecyl-3-carboxypropionyl)acetylhydrazide, sodium salt

53. 2-{2-[(4-(phenyl)phenylamino)-2-oxoacetamido]phenoxy}acetylhydrazide

54.2-{4-[(2-methoxy-4-(benzyl)phenylamino)-2-oxoacetamido]phenoxy}-N-(2-octylsuccinimido)acetylhydrazide

55.1,14-di{2-[(2-chlorophenylamino)-2-oxoacetamido]phenoxy}-3,4,11,12-tetraaza-2,5,10,13-tetraoxotetradecane

56.2-{4-[(2-(methoxycarbonyl)phenylamino)-2-oxoacetamido]-3-methylphenoxy}acetylhydrazide, cyclohexanone hydrazone.

Utility

The novel stabilizers of this invention are very effective additives forthe stabilization of polymeric compositions which are normally subjectto thermal and actinic light degradation. At times it may be beneficialto add extraneous additives generally referred to hereinafter which willact as synergists with the UV absorber groups of the compounds of thisinvention.

As used herein, the terms "polymer" and "polymeric composition(s)"include homopolymers or any type of copolymers.

One way in which the 2-(2-hydroxyphenyl)-2H-benzotriazole or oxanilidederivative stabilizers of the present invention can be used to stabilizepolymeric compositions against degradative effects of light is by merelymixing or blending with the polymeric composition a compound of thepresent invention in an amount effective to stablize the polymercomposition against the degradative effects of light. In this firstprocess of stabilizing polymers, the polymeric compositions need not be,and typically are not, coreactive with the stabilizers. Thus, thestabilizers of the present invention are effective UV stabilizers evenwhen mixed with inert polymers.

In addition to being useful in stabilizing inert polymeric compositions,the stabilizers of the present invention provide increased performanceand more long-term stabilization when they are in the form of reactiveadditives which coreact with the polymeric compositions to bestabilized. The hydrazide functionalized UV absorbers of the presentinvention (where Y is NH₂) are reactive additives that can be attachedto coreactive polymers to form polymer bound additives containingphotooxidative and thermaloxidative stabilizing groups. Once reactedwith the coreactive polymers, the stabilizer groups become chemicallybound to the polymers and will not be lost via volatilization, migrationor extraction. Non-limiting examples of coreactive polymers are thosewhich include ester, epoxide or anhydride groups, regardless of whethersuch groups form part of the polymer backbone, are at the end of thepolymers or are pendant from the polymer backbone.

Thus, this second aspect of the present invention relates to a polymericcompound comprising the reaction product of (a) a polymer containing atleast one ester, epoxide or anhydride functional group, or combinationsthereof, in the polymer backbone, on grafted side chains, as a pendantunit or combinations thereof and (b) a UV absorber compound of FormulasI or II where R¹² is hydrogen, R¹³ is hydrogen, Q is a direct bond and xand z are not 0.

The novel compounds of Formula III are ester precursors used asintermediates to make certain hydrazides of Formula I havingcorresponding structures and substituents.

The novel stabilizers of this invention can be blended with variouspolymeric compositions in high concentrations to form masterbatcheswhich can then be blended with additional polymer either of the same ordifferent type.

The amount of stabilizer used to stabilize the polymeric compositionwill depend on the particular polymer system to be stabilized, thedegree of stabilization desired and the presence of other stabilizers inthe composition. Normally it is advisable to have about 0.01% to about5% by weight of the UV absorber moiety of the compound of this inventionpresent in the polymeric composition. An advantageous range is fromabout 0.05% to about 3% by weight of the UV absorber portion of themolecule in the final composition. In some cases about 0.5% to about 1%by weight is sufficient.

Non-limiting examples of polymeric compositions which may be stabilizedby the stabilizer compounds of the present invention include:

1. Polyolefins, such as high, low and linear low density polyethylenes,which may be optionally crosslinked, polypropylene, polyisobutylene,poly(methylbutene-1), polyacetylene and, in general, polyolefins derivedfrom monomers having from 2 to about 10 carbon atoms, and mixturesthereof.

2. Polyolefins derived from diolefins, such as polybutadiene andpolyisoprene.

3. Copolymers of monoolefins or diolefins, such as ethylene-propylene,propylenebutene-1, propylene-isobutylene and ethylenebutene-1 copolymer.

4. Terpolymers of ethylene and propylene with dienes (EPDM), such asbutadiene, hexadiene, dicyclopentadiene and ethylidene norbornene.

5. Copolymers of alpha-olefins with acrylic acid or methacrylic acids ortheir derivatives, such as ethylene-acrylic acid, ethylene-methacrylicacid and ethylene-ethyl acrylate copolymers.

6. Styrenic polymers, such as polystyrene (PS) andpoly(p-methylstyrene).

7. Styrenic copolymers and terpolymers such as styrene-butadiene (SBR),styrene-allyl alcohol and styrene-acrylonitrile (SAN),styrene-acrylonitrile-methacrylate terpolymer, styrene-butadiene-styreneblock copolymers (SBS), rubber modified styrenics such asstyrene-acrylonitrile copolymers modified with acrylic ester polymer(ASA), graft copolymers of styrene on rubbers, such as polybutadiene(HIPS), polyisoprene or styrene-butadiene-styrene block copolymers(Stereo™ available from Firestone Synthetic Rubber and Latex Co.), graftcopolymers of styrene-acrylonitrile on rubbers, such as butadiene (ABS),polyisoprene or styrene-butadiene-styrene block copolymers, graftcopolymers of styrene-methyl methacrylate on rubbers, such aspolybutadiene (MBS), butadiene-styrene radial block copolymers (e.g. KRO3™ of Phillips Petroleum Co.), selectively hydrogenatedbutadiene-styrene block copolymers (e.g. Kraton G™ from Shell ChemicalCo.), and mixtures thereof.

8. Polymers and copolymers derived from halogen-containing vinylmonomers, such as poly(vinyl chloride), poly(vinyl fluoride),poly(vinylidene chloride), poly(vinylidene fluoride),poly(tetrafluoroethylene) (PTFE), vinyl chloride-vinyl acetatecopolymers, vinylidene chloride-vinyl acetate copolymers andethylenetetrafluoroethylene copolymers.

9. Halogenated rubbers, such as chlorinated and/or brominated butylrubbers or polyolefins and fluoroelastomers.

10. Polymers and copolymers derived from alpha, beta-unsaturated acids,anhydrides, esters, amides and nitriles or combinations thereof, such aspolymers or copolymers of acrylic and methacrylic acids, alkyl and/orglycidyl acrylates and methacrylates, acrylamide and methacrylamide,acrylonitrile, maleic anhydride, maleimide, the various anhydridecontaining polymers and copolymers described in this disclosure,copolymers of the polymers set forth in this paragraph and variousblends and mixtures thereof, as well as rubber modified versions of thepolymers and copolymers set forth in this paragraph.

11. Polymers and copolymers derived from unsaturated alcohols or theiracylated derivatives, such as poly(vinyl alcohol), poly(vinyl acetate),poly(vinyl stearate), poly(vinyl benzoate), poly(vinyl maleate),poly(vinyl butyral), poly(allyl phthalate), poly(allyl diethylene glycolcarbonate) (ADC), ethylene-vinyl acetate copolymer and ethylene-vinylalcohol copolymers.

12. Polymers and copolymers derived from unsaturated amines, such aspoly(allyl melamine).

13. Polymers and copolymers derived from epoxides, such as polyethyleneoxide, polypropylene oxide and copolymers thereof, as well as polymersderived from bis-glycidyl ethers.

14. Poly(phenylene oxides), poly(phenylene ethers) and modificationsthereof containing grafted polystyrene or rubbers, as well as theirvarious blends with polystyrene, rubber modified polystyrenes or nylon.

15. Polycarbonates and especially the aromatic polycarbonates, such asthose derived from phosgene and bisphenols such as bisphenol-A,tetrabromobisphenol-A and tetramethylbisphenol-A.

16. Polyester derived from dicarboxylic acids and diols and/orhydroxycarboxylic acids or their corresponding lactones, such aspolyalkylene phthalates (e.g. polyethylene terephthalate (PET),polybutylene terephthalate (PBT), and poly(1,4-dimethylcyclohexaneterephthalate) or copolymers thereof) and polylactones such aspolycaprolactone.

17. Polyarylates derived from bisphenols (e.g. bisphenol-A) and variousaromatic acids, such as isophthalic and terephthalic acids or mixturesthereof.

18. Aromatic copolyester carbonates having carbonate as well as esterlinkages present in the backbone of the polymers, such as those derivedfrom bisphenols, iso- and terephthaloyl chlorides and phosgene.

19. Polyurethanes and polyureas.

20. Polyacetals, such as polyoxymethylenes and polyoxymethylenes whichcontain ethylene oxide as a comonomer.

21. Polysulfones, polyethersulfones and polyimidesulfones.

22. Polyamides and copolyamides which are derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactones, such as the following nylons: 6, 6/6, 6/10, 11and 12.

23. Polyimides, polyetherimides, polyamideimides and copolyetheresters.

24. Cross-linked polymers which are derived from aldehydes on the onehand and from phenols, ureas and melamine on the other hand, such asphenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.

25. Alkyl resins, such as glycerolphthalic acid resins and mixturesthereof with melamine-formaldehyde resins.

26. Blends of vinyl monomers and unsaturated polyester resins which arederived from copolyesters of saturated and unsaturated dicarboxylicacids with polyhydric alcohols, as well as from vinyl compounds(crosslinking agents) and also halogen-containing, flame resistantmodifications thereof.

27. Natural polymers, such as cellulose and natural rubber, as well asthe chemically modified homologous derivatives thereof, such ascellulose acetates, cellulose propionate, cellulose butyrate and thecellulose ethers, such as methyl and ethyl cellulose.

In addition, the novel stabilizers of this invention may be used tostabilize various combinations or blends of the above polymers orcopolymers. They are particularly useful in the stabilization ofpolyolefins, acrylic coatings, styrenics, rubber modified styrenics,poly(phenylene oxides) and their various blends with styrenics,rubber-modified styrenics or nylon.

The novel ultraviolet light absorbers of this invention can be usedtogether with other additives to further enhance the properties of thefinished polymer. Examples of other additives that can be used inconjunction with the stabilizers of this invention include antioxidants,such as alkylated monophenols, alkylated hydroquinones, hydroxylatedthiodiphenyl ethers, alkylidene-bisphenols, hindered phenolic benzylcompounds, acylaminophenols, esters of3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid, esters of3-(5-t-butyl-4-hydroxy-3-methylphenyl)propionic acid,3(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid amides; other UVabsorbers and light stabilizers such as 2-hydroxybenzophenones,benzylidene malonate esters, esters of substituted or unsubstitutedbenzoic acids, diphenyl acrylates, nickel chelates, oxalic aciddiamides, and hindered amine light stabilizers; other additives such asmetal deactivators, phosphites and phosphonites, peroxide decomposers,fillers and reinforcing agents, plasticizers, lubricants, corrosion andrust inhibitors, emulsifiers, mold release agents, carbon black,pigments, fluorescent brighteners, both organic and inorganic flameretardants and nondripping agents, melt flow improvers and antistaticagents. Numerous examples of suitable additives of the above type aregiven in Canadian Patent No. 1,190,038.

Preparative Methods

The novel UV absorber hydrazides are prepared by reacting UVabsorber-substituted carboxylic acid esters and halides, sulfonic acidesters and sulfonyl halides with hydrazine or hydrazine hydrate.Typically the ester is dissolved in a polar solvent and converted to thedesired hydrazide by stirring with an equivalent amount or slight excessof hydrazine or hydrazine hydrate. The reaction may proceed at roomtemperature or may require heating. Preferably, the hydrazinolysisreaction is carried out in methanol or ethanol at about 10° C. to about30° C., but other solvents, such as isopropanol or ethylene glycol, arealso acceptable. In most cases the resulting hydrazides can be purifiedby recrystallization from the lower alcohols. Substituted hydrazides canbe prepared by reacting the esters with substituted hydrazines.

Suitable benzotriazole-substituted carboxylic acid esters andoxanilide-substituted carboxylic acid esters are described in U.S. Pat.Nos. 3,218,332 and 3,906,966, British Patent Application PublicationNos. 2,197,318 A, 2,188,631 A and 2,196,966 A, and French Patent No.1,506,632. Other benzotriazole-substituted carboxylic acid esters andoxanilide-substituted carboxylic acid esters may be prepared accordingto the following examples.

A. Reacting hydroxy, amino or thio substituted benzotriazoles withchloro-substituted or bromo-substituted acid esters in the presence ofan acid acceptor (e.g. potassium carbonate, tertiary amine) andoptionally in the presence of alkylation catalysts (e.g. aminopyridines,potassium iodide): ##STR6## where Z' is --O--, --N(R⁷)-- or --S--, R islower alkyl of 1-4 carbons or phenyl and R¹ and R⁴ are as previouslydefined.

B. Esterifying benzotriazole-substituted acids and oxanilide-substitutedacids. The preparation of such acids and esters are described in U.S.Pat. Nos. 3,399,173, 3,766,205, 3,629,191, 3,862,087, 3,214,436 andEuropean Patent Application Publication No. 57,160. ##STR7## where R' islower alkyl of 1-4 carbons or allyl, and R¹, R² and R⁴ are as previouslydefined.

C. Reacting aminoalkyl-substituted benzotriazoles with mono ester acidchlorides of dicarboxylic acids. ##STR8## where R', R¹, R² and R¹⁰ areas previously defined. Esters of this type, where R¹⁰ is 1,2-ethanediylare disclosed in U.S. Pat. No. 3,629,192. When R¹⁰ is a direct bond,such esters may also be prepared by reaction with a lower dialkyloxalate or diphenyl oxalate. ##STR9## where R, R¹ and R² are aspreviously defined. The preparation of the aminoalkyl-substitutedbenzotriazoles are described in U.S. Pat. Nos. 3,862,087 and 3,629,192.

D. Reacting amino-substituted-benzotriazoles and oxanilides with monoester acid chlorides of dicarboxylic acids. ##STR10## Theamino-substituted benzotriazoles are described in U.S. Pat. Nos.3,272,891 and 3,159,646.

Non-limiting examples of suitable hydrazines include hydrazine,hydrazine hydrate, 35-85% hydrazine hydrate, methylhydrazine,ethylhydrazine, propylhydrazine, isopropylhydrazine, n-butylhydrazine,sec-butylhydrazine, n-amylhydrazine, sec-amylhydrazine, n-hexylhydrazineand n-octylhydrazine, t-butylhydrazine, phenylhydrazine, benzylhydrazineand sec-octylhydrazine.

Hydrazone derivatives of this invention are prepared by reacting thehydrazides with ketones, aldehydes or formaldehyde in inert solvents,preferably in hydrocarbon solvents under azeotropic conditions. They mayalso be prepared by reacting hydrazones of ketones or aldehydes with UVabsorber-containing esters.

The novel carbamoyl and thiocarbamoyl derivatives are prepared byreacting the hydrazides with isocyanates, disocyanates, isothiocyanatesor diisothiocyanates in aprotic polar solvents, such as tetrahydrofuranor dimethylformamide.

The reactions of hydrazides with ketones, aldehydes, isocyanates,diisocyanates, isothiocyanates, and diisothiocyanates are well known inthe art and can occur under a wide variety of temperatures, times,solvents and concentrations Generally a mole ratio of 0.9:1.0 to 1.1:1.0of the hydrazide to the monofunctional coreactant is employed. If thecoreactant is difunctional, then a mole ratio of 1.8:2.0 to 1.1:1.0 ofthe hydrazide to the difunctional coreactant is employed. If thecoreactant is a compound that can easily be removed from the product,e.g. acetone or methyl ethyl ketone, lower mole ratios may be desirable.The coreactant may be used as the solvent.

The hydrazides also react with unsubstituted or N-substituted amino acidesters in lower alcohol solutions to form 1,2-amoyl hydrazines. Thereactions are normally carried out in refluxing alcohol (i.e. methanol)but may be carried out in higher boiling aprotic solvents or withoutsolvent by heating a mixture of the two components above their meltingpoints. The methyl and ethyl esters of N-substituted oxamates andsuccinamates are the preferred coreactants.

The novel acyl derivatives of the hydrazide may be prepared by reactingthe esters with acid hydrazides in refluxing alcohol (i.e. methanol).

The novel alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl andaralkoxycarbonyl derivatives of the hydrazides may be prepared byreacting the ester (as described above) with the corresponding alkyl,cycloalkyl, aryl or aralkyl carbazates in refluxing alcohol (i.e.methanol). Alternately, these derivatives may be prepared by reactingthe hydrazide with a disubstituted carbonate or substituted haloformate.When a haloformate is used, an additional base (inorganic or amine) maybe used to react with the halogen acid formed.

The novel sulfonyl derivatives of the hydrazides may be prepared byreacting the esters with the corresponding sulfonyl hydrazide.

The novel alkyl derivatives of the hydrazides may be prepared byreacting the hydrazides with epoxides. The reactions are generallycarried out neat or in a minimum amount of a high boiling solvent.Reaction generally occurs quite readily at about 140° C. to about 150°C.

The hydrazide group reacts with two equivalents of epoxide. The ratio ofthe unsubstituted hydrazide to the monoalkylated and dialkylatedproducts is dependent upon the mole ratio of epoxide to hydrazide, thetemperature and the concentration, if the reaction is run in a solvent.

Non-limiting examples of suitable ketones include acetone, methyl ethylketone, 2-pentanone, 2-hexanone, 3-hexanone, 2-decanone,3-methyl-2pentanone, 4-methyl-2-pentanone,4-methoxy-4-methyl-2-pentanone, cyclopentanone, cyclohexanone,2,4-dimethyl-4-heptanone, 3,5-dimethyl-4-heptanone,2,4-dimethyl-3-pentanone, 1,3-diphenylacetone, 2-octanone, 3-octanone,dihydroisophorone, 4-t-butylcyclohexanone, methyl cyclohexyl ketone,acetophenone, 2,2,6,6-tetramethyl-4-piperidone and2,6-diethyl-2,3,6-trimethyl-4-piperidone.

Non-limiting examples of suitable aldehydes include formaldehyde,acetaldehyde, butyraldehyde, dodecyl aldehyde, 2ethylbutyraldehyde,heptaldehyde, isobutyraldehyde, isovaleraldehyde, octyl aldehyde,propionaldehyde, benzaldehyde, 3,5-di-t-butyl-4-hydroxybenzaldehyde,2,3-dimethyl-p-anisaldehyde, 3-hydroxybenzaldehyde, 1-naphthaldehyde,salicylaldehyde, p-tolualdehyde and 2,3,4-trimethoxybenzaldehyde.

Non-limiting examples of suitable isocyanates include allyl isocyanate,benzyl isocyanate, n-butyl isocyanate, sec-butyl isocyanate, isobutylisocyanate, t-butyl isocyanate, cyclohexyl isocyanate, ethyl isocyanate,isopropyl isocyanate, 4-methoxyphenyl isocyanate, methyl isocyanate,octadecyl isocyanate, 1-naphthyl isocyanate, phenyl isocyanate, o-tolylisocyanate, m-tolylisocyanate and p-tolyl isocyanate,dimethyl-m-isopropenylbenzyl isocyanate and 2-isocyanatoethylmethacrylate.

Non-limiting examples of suitable isothiocyanates include allylisothiocyanate, benzyl isothiocyanate, 4-bromophenyl isothiocyanate,n-butyl isothiocyanate, sec-butyl isothiocyanate, isobutylisothiocyanate, t-butyl isothiocyanate, 3-chlorophenyl isothiocyanate,cyclohexyl isothiocyanate, ethyl isothiocyanate, methyl isothiocyanate,propyl isothiocyanate, isopropyl isothiocyanate, 1-naphthylisothiocyanate, t-octyl isothiocyanate, phenethyl isothiocyanate, phenylisothiocyanate, propyl isothiocyanate, o-tolyl isothiocyanate, m-tolylisthiocyanate and p-tolyl isothiocyanates.

Non-limiting examples of suitable amino acid esters include methyloxamate, ethyl oxamate, propyl oxamate, isopropyl oxamate, n-butyloxamate, phenyl oxamate, methyl succinamates, ethyl succinamate, propylsuccinamate, isopropyl succinamate, n-butyl succinamate, phenylsuccinamate, ethyl N-(2,2,6,6-tetramethyl-4-peridinyl)oxamate, methylN-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate, ethylN-2,2,6,6-tetramethyl-4-piperidinyl)succinamate, methylN-(2,2,6,6-tetramethyl-4-peridinyl)succinamate, ethylN-(3,5-di-t-butyl-4-hydroxyphenyl)oxamate, methylN-(3,5-di-t-butyl-4-hydroxyphenyl)oxamate, ethylN-(3,5-di-t-butyl-4-hydroxyphenyl)succinamate and methylN-(3,5-di-t-butyl-4-hydroxyphenyl)succinamate.

Non-limiting examples of suitable acid hydrazides include acetylhydrazide, propionic tydrazide, butyric hydrazide, isobutyrichydrazide,valeric hydrazide, isovaleric hydrazide, caproic hydrazide, decanoichydrazide, lauric hydrazide, stearic hydrazide, benzhydrazide,3,5-di-t-butyl-4-hydroxybenzhydrazide,3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid hydrazide,3-(n-hexylthio)propionic acid hydrazide,(4-benzoyl-3hydroxyphenoxy)acetyl hydrazide and3-(dimethylaminoethylthio)propionic acid hydrazide.

Non-limiting examples of suitable carbazates include ethyl carbazate,methyl carbazate, propyl carbazate, isopropyl carbazate, butylcarbazate, cyclohexyl carbazate, cyclopentyl carbazate, cyclododecylcarbazate, phenyl carbazate, benzyl carbazate, 4-t-butylcyclohexylcarbazate, 2-ethylhexyl carbazate, 4-methylphenyl carbazate and3-methoxyphenyl carbazate.

Non-limiting examples of suitable diaryl carbonates include diphenylcarbonate, di-(4-methylphenyl) carbonate, di-(3-methylphenyl) carbonate,di-(3-methoxyphenyl) carbonate, di-(2,6-dimethylphenyl) carbonate anddi-(2,5-di-t-butylphenyl) carbonate.

Non-limiting examples of suitable sulfonyl halides includebenzenesulfonyl hydrazide, 4-bromobenzenesulfonyl hydrazide,1-butanesulfonyl hydrazide, 4-t-butylbenzenesulfonyl hydrazide,p-toluenesulfonyl hydrazide, ethanesulfonyl hydrazide, methanesulfonylhydrazide, 4-fluorobenzenesulfonyl hydrazide, 1-hexadecanesulfonylhydrazide, isopropanesulfonyl hydrazide and 1-naphthalenesulfonylhydrazide.

Non-limiting examples of suitable epoxides include 1,2-epoxybutane,2,3-epoxybutane, 1,2-epoxycyclododecane,1,2-epoxycyclohexane,1,2-epoxyoctane, 1,2-epoxydecane,1,2-epoxydodecane, 1,2-epoxyoctadecane, 1,2-epoxy-3-phenoxypropane,2,3-epoxypropyl acrylate, 2,3-epoxypropyl methacrylate, 2,3-epoxypropyl4-methoxyphenyl ether, glycidyl isopropyl ether, glycidyl n-hexyl ether,glycidyl dodecyl ether and glycidyl octadecyl ether.

The following examples are presented to provide a more detailedexplanation of the present invention and are intended as illustrationsand not limitations of the invention. Unless otherwise stated herein,the temperatures are in degrees Centigrade and all parts are by weight.

EXAMPLE I Preparation of2-(2-[(phenylamino)-2-oxoacetamido]phenoxy)acetyl hydrazide

Into a 125 ml flask were placed 5phenyl-N'-(2-[ethoxycarbonylmethoxy]phenyl)oxamide (2.0 g, 0.006 mole),35 ml methanol, 35 ml tetrahydrofuran (THF) and 10 ml 54% aqueoushydrazine. The mixture was stirred at room temperature for 2 hrs. duringwhich time a solid precipitated. The solid was isolated by filtration,slurried with 150 ml water and filtered, then slurried with 75 mlmethanol and filtered again and air dried on the filter giving 1.0 g ofwhite solid (m.p. 183°-186° C.). The THF/methanol filtrate was strippedusing aspirator vacuum to give a tan solid residue. This residue wasslurried with 10 ml THF and filtered again. The solid was dried on thefilter giving 0.5 g of slightly tan solid (m.p. 179°-182° C.). Thesamples were shown to be the same by infrared spectra and were combined.The infrared spectrum showed an NH band at 3300 cm⁻¹ and carbonyl bandsat 1670 and 1600 cm⁻¹. The ester carbonyl of the starting material (1750cm⁻¹) was not present.

EXAMPLE 11 Preparation ofN-[(3-[2H-benzotriazol-2-yl]-2-hydroxy-4-methyl)benzyl]-3-piperidinecarboxylichydrazide A. Preparation of ethylN-[(3-[2H-benzotriazol-2-yl]-2-hydroxy-4-methyl)benzyl]-3-piperidinecarboxylate

2-(2-hydroxy-4-methylphenyl)-2H-benzotriazole (42.8 g, 0.19 mole) andn-butanol (50 ml) were slurried in a reaction flask under a nitrogenatmosphere at room temperature. Ethyl nipecotate (44.8 g, 0.28 mole) andparaformaldehyde (9.7 g, 0.32 equiv.) were added, the paraformaldehydeaddition causing as 4° C. rise in the temperature. The reaction washeated to 101° C. over 40 min. dissolving the solids. The reaction wasmaintained at this temperature for 24 hrs. The reaction mixture wasstirred with 250 ml water and 250 ml methylene chloride. The phases wereseparated and the organic phase washed twice with 200 ml portions ofwater. The organic solution was dried with anhydrous sodium sulfate andmagnesium sulfate and stripped using aspirator vacuum. The residualyellow oil weighed 104 g. Liquid chromatographic assay showed about 60%of the title compound, about 30% n-butanol and about 4% startingbenzotriazole. Upon prolonged cold storage, a solid precipitated. Someof this solid was isolated by filtration, slurried in methanol andfiltered, then washed with methyl t-butyl ether. The resulting slightlyyellow solid had a m.p. of 87°-90° C. The infrared spectra of both theoriginal oil and the isolated solid showed a carbonyl peak at 1720 cm⁻¹.

B. Preparation ofN-[(3-(2H-benzotriazol-2-yl)-2-hydroxy-4-methyl)benzyl]-3-piperidine-carboxylichydrazide

The crude ester prepared in Step A of this Example (84 g) was slurriedwith 100 ml methanol in a flask under nitrogen atmosphere at roomtemperature. Hydrazine hydrate (85% aqueous, 50 ml, 0.85 mole) was addedover 10 min. at 26°-29° C. The reaction was heated to reflux (77° C.)over 50 min., dissolving the ester. After refluxing 2.5 hrs., solidsbegan precipitating, thickening the reaction mixture. Additionalmethanol, 100 ml, was added and the mixture refluxed for a total of 11hrs. The mixture was stirred with 500-600 ml water and the solidisolated by filtration. The solid was slurried with 350 ml methylt-butyl ether and filtered, then washed with 250 ml water and filtered.The residual moisture was evaporated under reduced pressure. Theoff-white solid weighed 45.5 g and had a m.p. of 189°-192° C.

EXAMPLE III Preparation of2-([2-hydroxy-3-(2H-benzotriazol-2-yl)-5-methylphenyl]-methylamino)-2-oxoacetylhydrazide A. Preparation of ethyl2-([2-hydroxy-3-(2H-benzotriazol-2-yl)-5-methylphenyl]-methylamino)-2-oxoacetate

(1) From ethyl oxalyl chloride

2-(2-hydroxy-3-aminomethyl-5-methyl)-2H-benzotriazole (50.8 g, 0.2 mole)was slurried with 600 ml methylene chloride. Triethylamine (22.2 g, 0.2mole) was added. Ethyl oxalyl chloride (27.4 g, 0.2 mole) diluted with120 ml methylene chloride was added slowly over 20 min., causing thetemperature to rise from 23° C. to 38° C. The slurry was presentthroughout this addition, most solids dissolving shortly after completeaddition. The reaction was continued 18 hrs. at room temperature. Thereaction mixture was filtered of insolubles and transferred to aseparatory funnel and washed with 400 ml water, then 400 ml 5% aq. HCl(emulsion at interface), then 400 ml water (emulsion at interface). Theemulsified interfaces were isolated, diluted with water and the organicsolution which separated was returned to the main organic solution. Thesolvent was stripped under reduced pressure yielding a solid which waswashed with 600 ml methanol and dried on the filter. The product weighed55.5 g and had a melting point of 148°-152° C.

(2) From diethyl oxalate

Diethyl oxalate (8.8 g, 0.06 mole) was placed in a flask and dilutedwith 150 ml methanol.2-(2-Hydroxy-3-aminomethyl-5-methyl)-2H-benzotriazole (13.5 g, 0.05mole) was added and the solution stirred for 2 hrs. at room temperature,during which time the benzotriazole slowly dissolved and was replaced bythe precipitating product. The solid was filtered, rinsed with methanoland air dried. The product weighed 14.6 g and had a m.p. of 160°-166° C.

B. Preparation of2-{[2-hydroxy-3-(2-H-benzotriazol-2-yl)-5-methylphenyl]-methyl}amino-2-oxoacetylhydrazide

The ester prepared by either procedure (1) or (2) of Step A of thisExample (82.6 g, 0.23 mole) was slurried with 1200 ml methanol. To thiswas added 54% aq. hydrazine (27.3 g, 0.46 mole) and another 400 mlmethanol to facilitate stirring of the slurry. The reaction was allowedto stir for 2 hrs. The solid was filtered and the solid was air dried.The product weighed 94.9 g and had a m.p. of 256°-262° C. An infraredspectrum of the product showed two carbonyl peaks at 1625 and 1645 cm⁻¹.

EXAMPLE IV Preparation of3-[3-(2H-benzotriazol-2-yl)-4-hydroxy-5-t-butylphenyl]propionylhydrazide

Polyethylene glycol ester with3-[3-(2H-benzotriazol-2-yl)-4-hydroxy-5-t-butylphenyl]-propionic acid(Tinuvin 1130, a product of Ciba-Geigy) (332 g, about 0.51 mole) wasmixed with 335 ml methanol (two liquid phases). To this was added 54%aq. hydrazine (60 g, 0.1 mole). The reaction was heated to 40° C.,forming a homogeneous solution. This temperature was maintained for 1hr. and the progress followed by infrared spectroscopy (ester carbonylconverting to hydrazide carbonyl). The mixture was then refluxed for 3.5hrs. The solid which had formed was filtered and washed with 400 mlfresh methanol, giving 155.3 g product having a m.p. of 171°-175° C. Thefiltrate was checked by IR spectrum, showing unreacted ester. Thefiltrate was mixed with additional 54% hydrazine (10 g, 1.18 mole total)and refluxed for 1.5 hrs. The methanol wash from the above rinse wasconcentrated to about 100 ml and added to the refluxing filtrate. Thereaction was refluxed for 1 hr. more, then allowed to cool and standwhile the product precipitated. The product was filtered and air driedgiving another 36.0 g product having a m.p. of 172°-180° C.

EXAMPLE V Preparation of4-([2-hydroxy-3-(2H-benzotriazol-2-yl)-5-methylphenyl]-methylamino}-4-oxobutanoylhydrazide A. Preparation of Ethyl4-{[2-hydroxy-3-(2H-benzotriazol-2-yl)-5-methylphenyl]-methylamino}-4-oxobutanoate

Into a 250 ml flask were placed2-(2-hydroxy-3-aminomethyl-5-methylphenyl)-2H-benzotriazole (14.1 g,0.05 mole), 125 ml methylene chloride and triethylamine (6.0 g, 0.06mole). Ethyl succinyl chloride (8.6 g, 0.052 mole) diluted with 25 mlmethylene chloride was added slowly over 5 min. causing the temperatureto rise from 24° C. to 42° C. (refluxed). The reaction mixture wasstirred 30 min. at room temperature, heated to reflux and refluxed 30min. The reaction insolubles were filtered hot and the filtrate wastransferred to a 500 ml separatory funnel. It was washed with 100 mlwater, then 100 ml 5% aq. HCl (emulsion at interface), then 100 ml water(3 times until reaching a pH of 6). The solvent was stripped underreduced pressure, yielding a solid which was air dried. The productweighed 13.3 g, and had a melting point of 147°-150° C. The infraredspectrum showed a strong sharp OH band at 3310 cm⁻¹, a strong sharpcarbonyl band at 1640 cm⁻¹, and a medium broad carbonyl band at 1545cm⁻¹.

B. Preparation of4-{[2-hydroxy-3-(2H-benzotriazol-2-yl)-5-methylphenyl]-methylamino}-4-oxobutanoylhydrazide

The ester prepared in Step A of this Example (13.95 g, 0.038 mole) wasslurried in 150 ml of methanol in a 500 ml flask. Added to the ester was54% hydrazine (5 g, 0.084 mole). Shortly after addition the reactiongelled. Methanol (50 ml) was added to dilute the reaction. The reactionwas heated to reflux, and refluxed for 1.5 hrs., then cooled and allowedto stand 16 hrs. The reaction was again heated to reflux and refluxedfor 2 hrs. The insolubles were filtered from the hot (60° C.) solution.The filtrate was reduced in volume by distillation (144 ml removed) Thesolution was cooled to 60° C., and solids filtered. A precipitate formedin the filtrate and this was isolated by another filtration. Thecombined solids were air dried and weighed 1.5 g and had a m.p. of212°-216° C. The infrared spectrum showed a strong OH band at 3295 cm⁻¹,a strong sharp carbonyl band at 1635 cm⁻¹, and a medium sharp carbonylband at 1550 cm⁻¹, with a weak shoulder at 1510 cm⁻¹.

EXAMPLE VI Reaction of the Hydrazide of Example IV with 2-EthylhexylGlycidyl Ether

The hydrazide of Example IV (8.83 g, 0.025 mole) and 2-ethylhexylglycidyl ether (4.65 g, 0.025 mole) were combined in a flask withoutsolvent. The mixture was heated to 160° C., with the mixture liquifyingat 145° C. The mixture was heated for 1 hr. between 160°-170° C. Thereaction was cooled and slurried with 400 ml methanol. The solid thatwas formed (1.6 g) was removed by filtration. The methanol filtrate wasstripped under reduced pressure, leaving 8.6 g of a yellow, viscousliquid. Liquid chromatographic analysis of the product indicated it wasa mixture of the starting hydrazide and the monoalkylated anddialkylated products.

EXAMPLE VII Reaction of the Hydrazide of Example IV with Kraton FG 1910X™

Kraton FG 1901 X™ (a sytrene/butadiene block copolymer grafted with 2%maleic anhydride, a product of Shell Chemical Company) (30 0 g, 0.006maleic anhydride equiv.) was added to 300 ml of hot xylene (122° C.).After the polymer dissolved, the hydrazide of Example IV (2.2 g, 0.006mole) was added. The mixture was heated to reflux, and azeotropicallydistilled for 3 hrs. (no water formation noted). The xylene (125 ml) wasdistilled from the reaction. The mixture was cooled and stirred with 700ml methanol for 1 hr. The solids which formed were filtered. The solidswere processed for 2 min. in 500 ml methanol using a Waring blender. Thesolids were filtered, giving a weight of 22.6 g. The infrared spectrum(nujol mull) showed an imide band at 1730 cm⁻¹.

EXAMPLE VIII Reaction of the Hydrazide of Example IV with Epolene E43™

Epolene E43™ (polypropylene grafted with 6-7% maleic anhydride, aproduct of Eastman Chemical Company) (50 g, 0.03-0.05 maleic anhydrideequiv.) was added to 300 ml hot stirred xylene (110° C.) in a flask.After the Epolene dissolved, the hydrazide of Example IV was slowlyadded at 120° C. The mixture was heated to reflux, azeotropicallydistilling off all the water (collected 0.7 ml) over 1.5 hrs. Thereaction mixture was clear yellow. The reaction was cooled and thesolvent stripped under pressure yielding a solid weighing 55.53 g andhaving a m.p. of 130°-136° C. The infrared spectrum (xylene solution)showed a strong sharp imide band at 1730 cm⁻¹, and a very weak amic acidband at 1755 cm⁻¹.

EXAMPLE IX Preparation of3-[3-(2H-benzotriazol-2-yl)-4-hydroxy-5-t-butylphenyl]-N'-(butylaminocarbonyl)propionylhydrazide

The hydrazide of Example IV (17 05 g, 0.05 mole) was diluted with 200 mlTHF in a 500 ml flask. Butyl isocyanate (5.0 g, 0.05 mole) diluted with25 ml THF was added to the hydrazide over 5 min. causing the temperatureto rise from 23° C. to 28° C. The mixture was heated to reflux, clearingthe initally milky white solution. The reaction was refluxed for 1 hr,then cooled to room temperature and stripped of solvent under reducedpressure to yield a solid weighing 20.4 g and having a m.p. of 166°-170°C. The infrared spectrum showed a strong carbonyl band at 1670 cm⁻¹ witha weak shoulder at 1655 cm⁻¹.

EXAMPLE X Preparation of the 2-Butanone Hydrazone of the Hydrazide ofExample IV

The hydrazide of Example IV (17.05 g, 0.05 mole) and 250 ml xylene werecombined in a flask. 2-Butanone (5.4 g, 0.075 mole) was added to thestirring solution. The mixture was heated to reflux over 1 hr, cooled,then heated to azeotropically distill for 2 hrs., until water stoppedcoming over (collected 0.5 ml). The solution was initially milky white,but turned clear at 105° C. The solution was cooled, and the solidfiltered. The filter cake was washed with hexane and dried, leaving apowder weighing 16.8 g, with a m.p. of 168°-173° C. The infraredspectrum (nujol mull) showed a strong carbonyl band at 1660 cm⁻¹.

EXAMPLE XI

Reaction of the Hydrazide of Example IV with PA-18™

PA-18™ (an octadecene-maleic anhydride copolymer product of ChevronChemical Company) (21.9 g, 0.0625 mole) was added to hot xylene (100°C.) in a 500 ml flask. The polymer solution was heated to 120° C. andthe hydrazide of Example IV (17.05 g, 0.05 mole) was added over 1 min.The mixture was azeotropically distilled for 1.5 hrs. (collected 0.8 gwater). The reaction was stripped under reduced pressure, yielding asolid weighing 35.3 g, and having a m.p. of 120°-124° C. The infraredspectrum (nujol mull) showed two strong sharp carbonyl bands at 1725cm⁻¹ and 1610 cm⁻¹.

EXAMPLE XII Reaction of the Hydrazide of Example IV with SMA 3000™

SMA 3000™ (a styrene/maleic anhydride copolymer product of ARCO ChemicalCompany) (26.8 g, 0.0654 mole) was added to 250 ml hot xylene (100° C.)in a 500 ml flask. The polymer was heated to 120° C. for the slowaddition of the hydrazide of Example IV (20.5 g, 0.06 mole). The mixturewas azeotropically distilled for 1.5 hrs. (collected 0.9 ml water). Thesolution was cooled to 100° C., then stripped of solvent under reducedpressure, yielding a solid that weighed 45.9 g, and had a m.p. of195°-199° C. The infrared spectrum (xylene solution) showed a strongsharp carbonyl band at 1725 cm⁻¹ (imide) and a weak carbonyl band at1780 cm⁻¹ (residual anhydride).

EXAMPLE XIII Preparation of3-[3-(2H-benzotriazol-2-yl)-4-hydroxy-5-t-butylpbenyl]-N-(2-octadecylsuccinimido)propanamide

Octadecyl succinic anhydride (17.6 g, 0.05 mole) was placed in a 500 mlflask and diluted with 75 ml xylene. The solution was heated toazeotropically distill for 1 hr then cooled to 20° C. Additional xylene(175 ml) was added. At 130° C., the hydrazide of Example IV (17.05 g,0.05 mole) was slowly added. The mixture was azeotropically distilledfor 2 hrs. The reaction was cooled and the solvent stripped off underreduced pressure, leaving a viscous liquid. The liquid was placed on dryice, causing solidification. The solid weighed 29.7 g, and had a m.p. of117°-121° C. The infrared spectrum (nujol mull) showed a strong sharpimide carbonyl band at 1730 cm⁻¹, with a shoulder at 1675 cm⁻¹.

EXAMPLE XIV Reaction of the Hydrazide of Example III with Epolene E43™

Epolene E-43™ (50 g, 0.018 mole) was added to 500 ml hot xylene (100°C.). The hydrazide of Example III (6.2 g, 0.018 mole) was added at 110°C. The reaction was azeotropically distilled for 1.5 hrs. (collected 0.6g water). The reaction mixture was cooled and the precipitate filtered.The product weighed 27.4 g and had a m.p. of 139°-144° C. The infraredspectrum (xylene solution) showed a weak anhydride band at 1775 cm⁻¹,also a weak imide band at 1735 cm⁻¹ with an amide shoulder at 1700 cm⁻¹.

EXAMPLE XVI Preparation of2-([2-hydroxy-3-(2H-benzotriazol-2-yl)-5-methylphenyl]methylamino)-2-oxo-N'-(3-carboxypropenoyl)aoetylhydrazide

Maleic anhydride (2.45 g, 0.025 mole) and 250 ml THF were combined in a500 ml flask equipped with a Dean Stark water separation assembly. Thehydrazide of Example III (8.5 g, 0.025 mole) was added accompanied by arise in temperature from 24° C. to 29° C. The mixture was heated toreflux and refluxed for 1 hr., then cooled. The solid was filtered andrinsed with 250 ml THF. The filtrate and the rinsing solvent were placedin a flask and heated. As the THF distilled, it was replaced with xylene(200 ml). When the solution temperature reached 135° C. the reaction waallowed to reflux 1 hour. The reaction mixture was cooled to 80° C. andthe solid was filtered and dried in air. The product weighed 7.5 g andhad a m.p. of 198°-210° C. The infrared specturm showed a strongcarbonyl band at 1635 cm⁻¹.

EXAMPLE XVI Preparation of2-([2-hydroxy-3-(2H-benzotriazol-2-yl)-5-methylphenyl]methylamino)-2-oxo-N-(2-octadecysuccinimido)acetamide

Octadecylsuccinic anhydride (17 6 g, 0.05 mole) and 250 ml xylene werecombined in a 500 ml flask equipped with a Dean Stark water separationassembly. The mixture was warmed to 100° C. for the incremental additionof the hydrazide of Example III (17.0 g, 0.05 mole). Each portion gelledthe reaction mixture and the temperature was raised to 130° C. betweenadditions to thin the mixture. After completion, the reaction wasrefluxed for 1 hr. (collected 1.1 ml water). The reaction mixture wascooled to 80° C. and the insolubles removed by filtration. Upon coolingto room temperature, some of the product precipitated and was isolatedby filtration, giving 6.9 g of solid with a m.p. of 104°-108° C. Thefiltrate was stripped under reduced pressure, leaving a viscous liquid.The liquid was solidified by cooling on dry ice for 30 min. The finelight yellow solid weighed 19.0 g and had a m.p. of 106°-110° C. Thecombined product weighed 25.9 g. The infrared spectrum (xylene solution)showed two sharp carbonyl bands at 1735 and 1685 cm⁻¹.

EXAMPLE XVII Preparation of2-([2-hydroxy-3-(2H-benzotriazol-2-yl)-5-methylphenyl]methylamino)-2-oxo-N'-(butylaminocarbonyl)acetylhydrazide

The hydrazide of Example III (8.6 g, 0.025 mol) was slurried with 200 mlTHF in a 500 ml flask. Butyl isocyanate (2.5 g, 0.025 mole) in 25 ml THFwas added and the mixture heated to reflux for 3 hrs. The mixture wascooled and the solid filtered. The solid was allowed to air dry yielding8.0 g of product having a m.p. of 201°-203° C. The infrared spectrumshowed a weak carbonyl band at 1725 cm⁻¹ and two strong carbonyl bandsat 1690 and 1645 cm⁻¹.

EXAMPLE XVIII Preparation of2-([2-hydroxy-3-(2H-benzotriazol-2-yl)-5-methylphenyl]methylamino)-2-oxo-N'-(octadecylaminocarbonyl)acetylhydrazide

The hydrazide of Example III (8.6 g, 0.025 mol) was slurried with 250 mlTHF in a 500 ml flask. Octadecyl isocyanate (7.4 g, 0.025 mole) in 25 mlTHF was added and the mixture stirred at room temperature for 30 min.,then heated to reflux for 2 hrs. The mixture was filtered hot (100° C.).The solid weighed 8.1 g and had a m.p. of 185°-190° C. Upon standing,additional solid precipitated from the filtrate. This, too, was isolatedby filtration, giving 2.1 g more product with a m.p. of 185°-190° C.(total product 10.2 g). The infrared spectra of the two samples agreed,each having two strong sharp carbonyl bands at 1635 and 1685 cm⁻¹ with ashoulder at 1720 cm⁻¹.

EXAMPLE XIX Reaction of the Hydrazide of Example III with PA-18™

Xylene (300 ml) was heated to 100°-110° C. in a 500 ml flask equippedwith a Dean Stark water separation assembly. PA-18™ (21.9 g, 0.0625maleic anhydride equiv.) was added. The mixture was cooled to 80° C. forthe addition of the hydrazide of Example III (17.0 g, 0.05 mole)incrementally over 90 minutes, allowing the hydrazide to dissolvebetween portions. After half the hydrazide was added, the reaction washeated to reflux to remove the water that formed. The reaction wascooled to 120° C. for the addition of the remaining hydrazide. Thereaction was refluxed with azeotropic removal of water for 2 hrs. Thereaction was cooled to 120° C. and the insolubles filtered, then cooledto room temperature and filtered again. The filtrate was stripped ofsolvent under reduced pressure to give 35.2 g of product having a m.p.of 156°-160° C. The infrared spectrum showed a weak carbonyl band at1780 cm⁻¹ (anhydride) and strong carbonyl bands at 1730 and 1685 cm⁻¹.

EXAMPLE XX Reaction of the Hydrazide of Example II with PA-18™

PA-18™ (11.0 g, 0.031 maleic anhydride eq.) was dissolved in 250 ml hotxylene in a 500 ml flask equipped with a Dean Stark water separationassembly. The polymer solution was heated to reflux for the addition ofthe hydrazide of Example II (9.5 g, 0.025 mole) in 3 portions over 30min. After the addition, the reaction was azeotropically distilled toremove water for 90 min. (0.4-0.45 ml water collected). The solution wascooled to 100° C. and the solvent stripped under reduced pressure. Theresidue weighed 20.7 g and was pulverized in a mortar and pestle to forma light yellow powder (18.8 g). The infrared spectrum (xylene solution)showed a strong carbonyl band at 1725 cm⁻¹ (imide).

The present invention may be embodied in other specific forms withoutdeparting from the spirit or essential attributes thereof and,accordingly, reference should be made to the appended claims, ratherthan to the foregoing specification as indicating the scope of theinvention.

We claim:
 1. A polymeric compound comprising the reaction product of apolymer containing(a) at least one ester, epoxide or anhydridefunctional group, or combinations thereof, in the polymer backbone, ongrafted side chains, as a pendant unit or combinations thereof and (b) acompound of formula ##STR11## where R¹ is hydrogen, substituted orunsubstituted aliphatic of 1-8 carbons, substituted or unsubstitutedalkoxy of 1-8 carbons, substituted or unsubstituted alkoxycarbonyl of2-8 carbons, alkylaminocarbonyl of 2-5 carbons, dialkylaminocarbonyl of3-9 carbons, substituted or unsubstitutedN-(alkyl)-N-(aryl)aminocarbonyl of 8-15 carbons, alkoxysulfonyl of 1-4carbons, --C(═O)--OH--, --C(═O)NH₂, or --S(═O)₂ --OH;R² is hydrogen,substituted or unsubstituted aliphatic of 1-8 carbons, substituted orunsubstituted aryl of 6-14 carbons, substituted or unsubstitutedaraliphatic of 7-22 carbons, substituted or unsubstituted alkoxy of 1-8carbons, alkylaminocarbonyl of 2-5 carbons, dialkylaminocarbonyl of 3-9carbons, or substituted or unsubstituted N-(alkyl)-N-(aryl)aminocarbonylof 8-15 carbons; R³ is hydrogen, substituted or unsubstituted aliphaticof 1-20 carbons, substituted or unsubstituted araliphatic of 7-22cartons, or substituted or unsubstituted alicyclic of 5-12 carbons; R⁴,R⁵, R⁶ and R⁷ are independently hydrogen, hydroxy, substituted orunsubstituted aliphatic of 1-8 carbons, substituted or unsubstitutedaryl of 6-14 carbons, substituted or unsubstituted araliphatic of 7-22carbons, substituted or unsubstituted alkoxy of 1-12 carbons orsubstituted or unsubstituted alkylthio of 1-12 carbons, chloro, bromo,or substituted or unsubstituted alkoxycarbonyl or 2-8 carbons;X is X_(a)when attached to ring A, X_(b) when attached to ring B and X_(e) whenattached either ring E; X_(a) is a direct bond; X_(b) and X_(e) aredivalent radicals of formula --Z_(x) --R⁸ --{--N(R⁹)═O)]_(y) --R¹⁰--)_(z) --; Z is --O--, --N(R¹¹)--, --S--, or --S(═O)₂ --; x and z areindependently 1; y is independently 0 or 1; R⁸ is a direct bond orsubstituted or unsubstituted alkylene diradical of 1-4 carbons; R⁹ ishydrogen, substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted alicyclic of 5-12 carbons, substituted orunsubstituted aryl of 6-14 carbons, or substituted or unsubstitutedaraliphatic of 7-22 carbons; R¹⁰ is a direct bond, substituted orunsubstituted aliphatic diradical of 1-20 carbons, substituted orunsubstituted aryl diradical of 6-12 carbons, substituted orunsubstituted alicyclic diradical of 5-12 carbons, or substituted orunsubstituted araliphatic diradical of 7-22 carbons; R¹¹ is hydrogen,substituted or unsubstituted aliphatic of 1-20 carbons, substituted orunsubstituted alicyclic of 5-12 carbons, substituted or unsubstitutedaryl of 6-14 carbons, or substituted or unsubstituted araliphatic of7-22 carbons; n is 1; Y is ##STR12## R¹² is hydrogen; R¹³ is hydrogen,substituted or unsubstituted aliphatic of 1-20 carbons, substituted orunsubstituted alicyclic of 5-12 carbons, substituted or unsubstitutedaryl of 6-14 carbons, or substituted or unsubstituted araliphatic of7-22 carbons, and when alicyclic, R¹³ may optionally contain 1-6heteroatoms --O--, --S-- or --N(R²¹)--, with the proviso that multipleheteroatoms must be separated from each other and the chain ends by atleast one carbon atom; Q is a direct bond between the nitrogen and R¹³ ;R²¹ is hydrogen, aliphatic of 1 to 8 carbons, aliphatic acyl of 2-6carbons, or substituted or unsubstituted benzoyl; optional substituentsfor R¹, R², R³, R⁸, R⁹, R¹⁰, R¹¹, R¹³ and R²¹ are independently one ormore of the following: chloro, bromo, alkyl of 1-4 carbons, alkoxy of1-8 carbons, phenoxy, cyano, hydroxy, epoxy, carboxy, alkyoxycarbonyl of2-6 carbons, acyloxy of 1-4 carbons, acryloyl, acryloyoxy, methacryloyl,methacryloyoxy, hydroxymethyl, hydroxyethyl, alkylthio of 1-4 carbons ortrialkoxysilyl of 3-12 carbons; and additional optional substituents forR¹³ are aliphatic of 1-20 carbons, cycloaliphatic of 5-12 carbons, arylof 6-14 carbons, aralkyl of 7-22 carbons, alkoxy of 1-20 carbons,cycloalkoxy of 5-12 carbons, aryloxy of 6-14 carbons, aralkoxy of 7-15carbons, aliphatic acyloxy of 2-20 carbons, alicyclic acyloxy of 6-13carbons, aryl acyloxy of 7-15 carbons, or araliphatic acyloxy of 8-16carbons.
 2. The polymeric compound of claim 1 which is a reactionproduct of the polymer and(2-[(phenylamino)-2-oxoacetamido]phenoxy)acetyl hydrazide.
 3. Thepolymeric compound of claim 1 which is a reaction product of the polymerand2-([2-hydroxy-3-(2H-benzotriazol-2-yl)-5-methylphenyl]methylamini)-2-oxoacetylhydrazide.
 4. The polymeric compound of claim 1 which is a reactionproduct of the polymer and4-([2-hydroxy-3-(2H-benzotriazol-2-yl)-5-methylphenyl]methylamino)-4-oxobutanoylhydrazide.